NOTES
1833
rivat ives were prepared. Diphenyl-@-naphthylmethyl chloride was obtained by the action of hydrogen chloride on the carbinol. When the chloride was treated with molecular silver, the free radical, diphenyl@-naphthylmethyl, resulted. 2 . The radical was isolated in the crystalline state. A careful study was made of its reactions with oxygen, iodine and acids, and of the effect of light. The conductivity of the free radical, diphenyl-@-naphthylmethyl, was determined in sulfur dioxide. The conductivities of the *chlorides and bromides of triphenylmethyl, diphenyl-a-naphthylmethyl and diphenyl-P-naphthylmethylwere determined in both sulfur dioxide and hydrogen cyanide. These compounds, especially the bromides, were found to be good conductors. The molecular weight of diphenyl-@naph thylmethyl was determined in 8 solvents whose freezing points covered the range from -22” to +SO”. It was found that the hexa-arylethane was dissociated from 15% to 50%. 3. Experiments were carried out t o find what effect changes in concentration of the free radical would have upon the dissociation and upon the color of the solutions. It has been found that the resulting changes in color intensity are independent of the changes in dissociation. It has also been found that the changes in color intensity which result from variations in temperature are, again, not parallel to the changes in dissociation which are thus produced. These facts point t o the conclusion that color formation in solutions of free radicals is not due wholly to dissociation of the hexa-aryl ethane into the tri-aryl methyl. The most satisfactory explanation of the facts is the hypothesis that in addition to dissociation we have tautomerization of the benzenoid tri-arylmethyl into the quinonoid form. The equilibrium between the dimolecular and monomolecculal- forms on the one hand and the equilibrium between the two monomolecular tautomers on the other hand, are not equally influenced by changes either in concentration or in temperature. This investigation was made with the assistance of The National Aniline and Chemical Company Fellowship, and we wish t o express our obligations for the generous aid we have thus received. :INN
ARBOR,MICHIGAN
NOTES Addendum to “The Electron Theory of Valence as Applied to Organic Compounds.”’ I n order to avoid any misunderstanding the following considerations on the rupture of carbon valences by oxidation, asemphasized by the author in lectures on the subject, should be included in the discussion of oxidation and reduction of organic compounds in the above named article. The discussion was not intended t o be exhaustive but simply emphasized certain facts bearing on the subject. THISJOURNAL,46,1293 (1922).
1834
NOTES
It is worthy of note that the rupture of the union of two carbon atoms by oxidation-involving the loss of two electrons by one of the atoms or jointly by both-takes place with particular ease when we have two neighboring carbonyl groups-CO.CO--, as in oxalic acid, ortho-diketones, etc. In this case there are no “exposed” valences as in the oxidation o f an olefin t o a glycol, an aldehyde to an acid, etc., which were emphasized as the easiest form of oxidation. Rut it is noteworthy that the structure one. Thus for oxalic acid, we have2 is undoubtedly a highly . polar . H+-0- Xi ;C-r -0”‘H, and the high polarity of the field surrounding the -0- -0-
carbon atoms evidently loosens the union between the two and exposes the electrons held by them somewhat in the same way, but not going quite so far, as in the case of actual ionization in a similar field. For cyanogen N -r‘ +$ CT- C i ZX, the nitrile of oxalic acid, the effect, as is well known, goes so far that we have actual hydrolysis, exactly as for chlorine, potassium cyanide and potassium cyanate being formed by the action even of aqueous alkali through a rupture of the C+-Cunion. For dicarbonyl derivatives in general similar relations seem to underlie the break of a carbon chain with an escape of electrons. The effect of neighboring highly polar charges is seen also in the oxidation of alcohols to aldehydes and ketones, which is, as it should be, not a5 easily accomplished as the further oxida‘tion of an aldehyde to an acid. JULIUS
STIECLITZ
THEKENTCHEMICAL LABORATORY, OF CHICAGO, UNIVERSITY CHICAGO, ILLINOIS Received July 7 , 1922
A Modified Schiff’s Solution.-The writer has for some time desired a test solution for aldehydes which would overcome the patent objections to Schiff’s solution, and which would a t the same time have a chemical basis easily comprehended by the student of elementary organic chemistry. The objections to the use of Schiff’s solution are (1) it stains the hands and clothing, ( 2 ) it requires several hours for preparation, especially if carefully made, using the minimum amount of sulfur dioxide, and (3) it may not be heated, and one has constantly to warn students to prevent them from falling into this error. T’arious aldehyde tests arc mentioned in the literature but they are in general of a complex nature, and not so easily carried out as the Schiff test. For this reason, experiments were made to vary the “reducing” Ltxent used in thc Schiff 5olution. I t was round th,tt much better resulli c auld he o1,tainc.d by the 5ubstitutioii of sodium h!yowlfite for sulfur StiLAhtL,
“ ( ~ i i r i h tttri
t
. l i i < t l > 515,” ’1
hc C‘ciitiiry clo , 1911, vu1 11, g b3.d
dioxide. The solution niade as outlined in this paper is perfectly colorless, will not stain the container nor the hands, and there are no precautions necrssary for keeping it. It may be put in clear glass bottles and lcft unstoppered in the light. A very desirable feature is its ease of preparation; to make up a large quantity requires but a few minutes. If this solution is boiled for 1 minute (no longer) i t first becomes red, and then again practically colorless. It may now be heated in testing for aldehydes, in order to hasten the test. Used in this way the solution here described will give the aldehyde test in about half the time required for the ordinary Schiff test, although without heating the test is usually a little slower than with the Schiff solution. *4small amount of acid does not interfere with the test, but if the solution is to be heated, i t should first be made neutral to litmus. Directions for Preparation of Test Solution.-Rosaniline hydrochloride ( 0 (103 g.) is dissolved in 30 to 100 cc. of hot water, filtered if necessary, diluted to 300 cc. and the solution well cooled with running water. ’1‘0 the cooled solution is added ti g. of sodium hyposulfite (NazSs04). This will completely dissolve in a few minutes, after which the solution is ready for iise. In the tests with aldehydes given in the’l‘able 2 cc. of test solution was used, and about 2 drops of the substance beihg tested. The figures give the time in seconds for the development of a positive test. Schiff’s solution’ Sec.
Modified solution Sec
Mod. sol. previously boiled for 1 min. Sec
> 1 20 :Formaldehyde (405,{,).. . . . . . . . . 3-3 Acetaldehyde (conc.). . . . . . . . . . . 5 10 - faint 2&30 no test no test .bugenol ...................... no test no test .illy1 alcohol.. . . . . . . . . . . . . . . . . faint 20-23 1 Prepared from directions in hlulliken, “Identification of Pure Organic Compoimds,” J. Wiley and Sons, London, 1911, vol I, p. 15.
COLLEGEOF ARTSAND SCIENCES FAYETTEVILLE, ARKANSAS Received March 3 . 19’22
E. WERTHEIM
